High solids acrylic-based coatings

ABSTRACT

According to one aspect of the present invention, improved acrylic copolymer resins are provided which are formed by co-polymerization of a monomer mixture comprising hydroxy-substituted alkyl (meth)acrylates, alkyl methlacrylates or vinyl aromatics, and higher alpha-olefins. The invention provides improved low molecular weight acrylic resins useful as components in high solids acrylic coatings suitable for electrostatic spraying.

This is a continuation of application Ser. No. 807,586, filed 12/11/85,now abandoned.

CROSS-REFERENCE TO RELATED APPLICATION

This Application is related to co-pending application, Ser. No. 807,585filed 12-11-85 filed simultaneously herewith.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to a composition of acrylic resins forcoatings, adhesives, etc. and to a process for synthesis of the resins.

2. Description of the Prior Art

A large variety of acrylic coating compositions are known. Low solidscoatings, i.e., those containing about 18 to 40 wt% solids and thebalance solvents, have heretofore been developed in which the resinsthemselves are characterized by high molecular weights, e.g., molecularweights in the range of 20,000 to 40,000. Such high solventconcentrations are required with these high molecular weight resins inorder to supply flowability and other properties necessary for ease inapplying a uniform coating. Due to strict air pollution regulations,pollution abatement of solvents is of paramount importance. To this end,the industry has expended much effort in an attempt to developelectrostatically sprayable coatings containing high solids contents;that is, coatings having a lower amount of solvents in order to satisfypollution regulations. Attempts to achieve high solids coatings bymerely using more of the conventional high molecular weight resins inthe coatings have not been successful since the increased solids contentusing these resins results in an unacceptably high viscosity, and oftenthe larger amounts of the resins cannot themselves be dissolved. Effortsat developing a "super solvent" for these conventional high molecularweight resins have also not proved to be successful. One prior artapproach has been to formulate coatings containing low molecular weightresins (e.g., of about 1,000 to 7,000 weight average molecular weight)would be desirable in high solids coatings in order to reduce the amountof solvents necessary in the blending for coating applications and,hence, the pollution difficulties associated with the solventsthemselves. After application of the coatings to a surface, the coatingsare cured to form a polymeric network of higher molecular weight andenhanced physical properties. These high solids acrylic coatings areuseful as exterior finish for automobiles, trucks, metal furniture, andas an appliance finish.

K. K. Mitra, "Electrostatic Application of Paint", Paint India, vol. 29,no. 9, pp. 52-56 (1979) indicates that while non-polar solvents(aliphatic and aromatic hydrocarbons chlorinated solvents, terpenes,etc.) can be employed in electrostatically sprayable paints to increasebulk and resistivity, polar solvents are used to control resistivity.The polar group is said to include ketones, alcohols, esters, ethers,ether alcohols, and nitro paraffins, etc. The non-polar group is said toinclude aliphatic and aromatic hydrocarbons, chlorinated solvents,terpenes, etc.

Also illustrative of prior art, high solids acrylic resins are thosedisclosed in U.S Pat. No. 4,276,212 and in European Patent ApplicationNos. 27,719; 29,594 and 29,683.

Solvents which are indicated to be typical in these references (e.g.,those mentioned in European Patent Application No. 29,594) are: Toluene,xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl amylketone, methyl ethyl ketone, butyl alcohol and other aliphatic,cycloaliphatic and aromatic hydrocarbons, esters, ethers, ketones, andalcohols.

In a brochure entitled "Hexyl Acetate for the Coatings Industry" (EnjayChemical Company), published prior to 1980, use of hexyl acetate ascoating solvent in certain specific low solids acrylic coatingcompositions; in urethane coatings; in nitrocellulose coatings; and inbaking enamels was disclosed.

U.S. Pat. Nos. 4,075,242 and 4,276,432 disclose the preparation ofacrylic-based resins by use of polymerization media containing certainhigh boiling solvents and disclose the use of ethylene and propylene asco-monomers.

European Pat. No. 29,339 discloses the formation of bifunctionalcopolymers in which the monomers comprise from 5 to 25 wt% ofmonoethylenically unsaturated monomers having a glycidyl functionality,from 5 to 25% of monoethylenically unsaturated monomers having hydroxyfunctionality and 90 to 70 wt% of other monoethylenically unsaturatedmonomers, with acrylates as well as mixtures of acrylates and vinylhydrocarbons being preferred. Only monovinyl aromatic hydrocarbons areparticularly indicated as useful (e.g., styrene, alpha-methyl styrene,vinyl toluene, t-butyl styrene and chlorostyrene).

U.S. Pat. No. 4,369,296 relates to the production of methyl methacrylatehompolymers (or copolymers with certain copolymerizable vinyl monomers;e.g., styrene and alkyl-substituted styrene) in the presence of from0.01 to 10 wt% of enol ethers derived from aliphatic or cycloaliphaticaldehydes and ketones.

U.S. Pat. No. 3,271,375 relates to the use, in combination with a freeradical polymerizable material, of certain unsaturated heterocyclicorganic compounds as molecular weight regulators. The prior art hassought to control the degree of polymerization via chain transfercontent (in the preparation of acrylic oligomers for high solids coatingresins) by use of relatively inactive solvents such as alkyl aromatics,high boiling ethers and benzyl alcohol. D. Rhum, et al., J. CoatingsTech'n. Vol. 55, no. 703, 75-79 (August 1983).

U.S. Pat. No. 4,532,294 relates to the preparation of acrylic copolymerresins employing polymerization solvents comprising certain alkanoicacid alkyl esters for copolymerization of hydroxy-substituted alkyl(meth)acrylate and non-hydroxy substituted alkyl (meth)acrylatemonomers, and in optional presence of additional monomers comprisingmonovinyl aromatic hydrocarbons. Among the non-hydroxy substituted alkyl(meth)acrylate monomers which may be employed are (meth)acrylates aswell as mixtures of acrylates and vinyl hydrocarbons.

U.S. Pat. No. 3,926,925 relates to novel interpolymers containing anolefin (an alpha-olefin, a 2-alkyl-1-olefin and a vinyl aromatic) polarmonomers, such as an alkyl acrylate, and a fumarate ester or a maleicacid derivative which are prepared with a catalyst system of an alkylaluminum halide and an organic peroxide. U.S. Pat. No. 3,959,225 relatesto a thermally-staged process for preparing alternating interpolymers ofone or more polar monomers and one or more mono or polyolefins in whicha polar monomer-Lewis Acid complex is reacted with an olefin in thepresence of an active oxygen compound. The olefins disclosed as usefulin U.S. Pat. No. 3,959,225 are certain Type I olefins and Type IIIolefins.

U.S. Pat. No. 3,968,148 relates to oligomers of (i) about 10 to 90 wt%of 1-alkene; (ii) about 1 to 45 wt% of a straight or branched chainalkyl acrylate or (meth)acrylate in which the alkyl group contains 8 to34 carbon atoms; and (iii) 1 to about 35 wt% of an acrylic acid, esteror nitrile, or a mixture of such acids, esters, nitriles, and amido andamino derivatives.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, improved low molecularweight acrylic copolymer resins capable of cross-linking are provided byfree-radical co-polymerization of a mixture of (i) at least one numberselected from the group consisting of (meth)acrylic acid andhydroxy-substituted alkyl (meth)acrylates, (ii) at least one non-hydroxysubstituted monomer selected from the group consisting of vinyl aromatichydrocarbons and lower alkyl esters of methacrylic acid, and (iii) atleast one alpha-olefin having from 7 to 20 carbon atoms per molecule.These low molecular weight acrylic resins are particularly useful ascomponents in adhesives and in high solids acrylic coatings suitable forelectrostatic spraying.

Low molecular weight acrylic copolymers find extensive application incoatings, adhesives, etc. The polymers are synthesized by free-radicalco-polymerization of monomers selected from the group comprising estersof acrylic and (meth) acrylic acids, styrene and its homologues,monomers bearing functional groups such as hydroxylalkyl acrylates and(meth)acrylates, acrylic and (meth)acrylic acids, glycidyl acrylate and(meth)acrylate, etc. in organic solvents.

We have found that all or at least a significant proportion of the alkylacrylates, such as ethyl acrylate, butyl acrylate, and 2-ethylhexylacrylate, which are used in coating resins to regulate Tg and impartflexibility to the coating films, can be substituted by C₇ -C₂₀alpha-olefins. This substitution can result in a reduction of molecularweight, improvement in color of the polymer solutions, and alsopotential improvement in the polymer's hydrophobocity, along with otherimportant polymer properties.

DETAILED DESCRIPTION OF THE INVENTION

The oligomers of this invention will comprise: (i) from about 5 L to 45wt% and preferably from about 10 to 35 wt%, at least one of the groupconsisting of (meth)acrylic acid and hydroxy-substituted alkyl(meth)acrylate monomers (Monomer A), (ii) from about 20 to 80 wt%,preferably from about 25 to 70 wt%, of the non-hydroxy monomer selectedfrom the group consisting of vinyl aromatic hydrocarbons and lower alkylester of methacrylic acid (Monomer B), (iii) from about 1 to 55 wt%,preferably from about 5 to 45 wt%, and more preferably from about 10 to40 wt%, at least one alpha-olefin having a total of from 7 to 20 carbonatoms (Monomer C), and (iv) from about 0 to 64 wt%, preferably fromabout 0 to 54 wt%, and more preferably from 0 to 40 wt%, of thenon-hydroxy monomer selected from the group of alkyl esters of acrylicacid (Monomer D), with the proviso that Monomers A and B be employed ina combined amount of at least 35 wt%, preferably from about 45 to 90wt%, and most preferably from about 55 to 80 wt%, of the total monomermixture, and with the further proviso that Monomers C and D be employedin a combined amount of less than 65 wt%.

The alpha-olefins suitable in this invention as a component of thepolymerization mixture comprise normally liquid aliphatic alpha-olefinshaving from 7 to 20 carbon atoms per molecule, and preferably from 8 to16 carbon atoms per molecule. The term "normally liquid", when appliedherein to such olefins, is intended to refer to olefins which are in theliquid state at ambient conditions (25° C., 1 atm). Suitable aliphaticalpha-olefins are branched and straight chain olefins with terminalolefinic unsaturation, and comprise compounds of the formula (I):##STR1## wherein Y¹, X¹ and X² are the same or different and are H oralkyl of from 1 to 17 carbon atoms, with the proviso that Y, X¹ and X²moieties contain a total of from 4 to 17 carbon atoms, preferably from 5to 13 carbon atoms, more preferably from 6 to 11 carbon atoms, and mostpreferably from 7 to 9 carbon atoms.

A preferred class of olefins for use in this invention are aliphaticalpha-olefins of the formula (II): ##STR2## wherein Y² is H or alkyl offrom 1 to 5 carbon atoms and wherein X³ and X⁴ are the same or differentand are H or alkyl of from 1 to 11 carbon atoms, with the proviso thatthe Y², X³ and X⁴ moieties contain a total of from 5 to 11 carbon atoms.

Such alkyl groups of formulae (I) and (II) may be branched or straightchained, and exemplary thereof are methyl, ethyl, n-butyl, iso-butyl,sec-butyl, tert-butyl, n-pentyl, iso-pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, and thelike. Exemplary of suitable aliphatic alpha-olefins, therefore, are1-heptene, 3-ethyl-1-pentene, 1-octene, 3-methyl-1-heptene,4-propyl-1-heptene, 1-nonene, 2-methyl-1-heptene, 1-decene, 1-undecene,1-dodecene, the terminally unsaturated tridecenes, tetradecenes,pentadecenes and hexadecenes, and the like. Such alkyl groups offormulae (I) and (II) may also be phenyl-substituted; e.g., phenylmethyl, 2-phenyl ethyl, 3-phenyl butyl and the like.

The selected alpha-olefin will preferably be characterized by a normalboiling point (i.e., at 1 atm) of at least about 100° C., morepreferably from about 115° to 250° C., and most preferably from about150° to 200° C. The alpha-olefin will also preferably be substantiallyfree of water and trace metals, as discussed below for thepolymerization solvent, when the resins to be formed are intended foruse as a component of electrostatic spray coatings.

Particularly preferred are mixed aliphatic alpha-olefins conventionallyproduced by ethylene oligomerization (i.e., the ethylene growthreaction).

The hydroxy-substituted alkyl (meth)acrylates which can be employed asMonomer A comprise members selected from the group consisting of thefollowing esters of acrylic or methacrylic acid and aliphatic glycols:2-hydroxy ethyl acrylate; 3-chloro-2-hydroxypropyl acrylate;1-hydroxy-2-acryloxy propane; 2-hydroxypropyl acrylate; 3-hydroxypropylacrylate; 2,3-dihydroxypropyl acrylate; 2-hydroxy-butyl acrylate;4-hydroxybutyl acrylate; diethylene-glycol mono-acrylate;5-hydroxypentyl acrylate; 6-hydroxyhexyl acrylate; triethyleneglycolmono-acrylate; 7-hydroxyphenyl acrylate; 1-hydroxy-2-methacryloxypropane; 2-hydroxy-propyl methacrylate; 3-hydroxypropyl methacrylate;2,3-dihydroxypropyl methacrylate; 2-hydroxybutyl methacrylate;3-hydroxybutyl methacrylate; 2-hydroxyethyl methacrylate; 4-hydroxybutylmethacrylate; 3,4-dihydroxybutyl methacrylate; 5-hydroxypentylmethacrylate; 6-hydroxyhexyl methacrylate; 1,3-dimethyl-3-hydroxybutylmethacrylate; 5,6-dihydroxyhexyl methacrylate; and 7-hydroxyheptylmethacrylate. Although one of ordinary skill in the art will recognizethat many different hydroxy-substituted alkyl (meth)acrylates includingthose listed above could be employed, the preferred hydroxy functionalmonomers for use in the resin of this invention are hydroxy-substituted(meth)acrylates, meaning alkyl acrylates and methacrylates having atotal of 5 to 7 carbon atoms, i.e., esters of C₂ -C₃ dihydric alcoholsand acrylic or methacrylic acids.

Most preferably, the hydroxy-substituted alkyl (meth)acrylate monomercomprises a compound of the formula (III): ##STR3## wherein R⁴ ishydrogen or methyl and R⁵ and R⁶ are independently selected from thegroup consisting of hydrogen and alkyl of from 1 to 6 carbon atoms.Illustrative of these particularly suitable hydroxy-substituted alkyl(meth)acrylate monomers are 2-hydroxy ethyl methacrylate, 2-hydroxyethylacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and2-hydroxypropyl methacrylate.

The Monomer A can also comprise (meth)acrylic acid; i.e., acrylic acidor methacrylic acid, or a mixture thereof alone or together with any ofthe aforementioned hydroxy-substituted alkyl (meth)acrylate monomers.

The non-hydroxy monomers (Monomer B) comprise at least one memberselected from the group consisting of vinyl aromatic hydrocarbonmonomers and alkyl methacrylate monomers.

The vinyl aromatic hydrocarbons comprise monovinyl aromatic hydrocarbonscontaining from 8 to 12 carbon atoms and halogenated derivatives thereofhaving halo-substituted aromatic moieties (including styrene,alpha-methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene andthe like).

The non-hydroxy substituted alkyl methacrylate monomers which may beemployed are methacrylates (as before, meaning esters of methacrylicacids). Preferred non-hydroxy unsaturated monomers are esters of C₁ -C₄monohydric alcohols and methacrylic acid, e.g., methylmethacrylate,ethylmethacrylate, butylmethacrylate, etc.

Particularly preferred are alkyl methacrylate monomers selected from thegroup consisting of monomers of the formula (IV): ##STR4## wherein R⁷ isalkyl of from 1 to 3 carbon atoms. Particularly preferred are ethylmethacrylate and methyl methacrylate.

The non-hydroxy substituted alkyl acrylate monomers which may beemployed as Monomer D are alkyl esters of acrylic acids. Preferrednon-hydroxy alkyl acrylates are esters of C₁ -C₄ monohydric alcohols andacrylic acid, e.g., methyl acrylate, ethyl acrylate, butyl acrylate, andthe like.

The monomer mixture can additionally include optional monomers such asvinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile,and vinyl acetate.

The total monomer mixture utilized in the polymerization process stepwill comprise (a) from about 5 to 45 wt%, and preferably from about 10to 35 wt%, of Monomer A, (b) from about 20 to 80 wt%, preferably fromabout 25 to 70 wt% of Monomer B, and (c) from about 1 to 55 wt, morepreferably from about 5 to 45 wt%, and most preferably from about 10 to40 wt%, of the above alpha-olefins, and (d) from 0 to 64 wt%, andpreferably from 0 to 54 wt%, of Monomer D, in addition to any optionalmonomers (discussed above). Generally, Monomer B will comprise a mixtureof (1) an alkyl methacrylate in an amount of from about 0 to 80 wt%,more preferably from about 15 to 50 wt%, of the total monomer mixture,and (2) a monovinyl aromatic hydrocarbon (e.g., styrene and alpha-methylstyrene) which will be employed in an amount of from about 0 to 80 wt%,preferably from about 10 to 40 wt% of the total monomer mixture. MonomerA will typically comprise a mixture of (1) a hydroxy-substituted alkylmeth-acrylate of formula III, which will be present in an amount of fromabout 5 to 45 wt%, more preferably from about 8 to 30 wt%, of the totalmonomer mixture, and (2) acrylic acid or methacrylic acid which will beemployed (alone or together) in an amount from about 0 to 20 wt%, morepreferably from about 1 to 15 wt%, of the total monomer mixture.However, the total amount of Monomers A and B should be at least 35 wt%,preferably from about 45 to 90 wt%, and most preferably from about 55 to80 wt%, of the total monomer mixture, and the total amount of Monomers Cand D should be less than 65 wt%, preferably from about 10 to 55 wt%,and most preferably from about 20 to 45 wt%, of the total monomermixture.

The remaining above-mentioned monomers may be present in an amount of upto 30 wt%, more typically from 3 to 10 wt%, of the monomer mixture,where employed.

The organic polymerization solvents which can be employed comprise atleast one member selected from the group consisting of ketones, ethers,glycols, glycol ethers, esters, keto ethers, ether esters, alcohols,nitro-substituted paraffins, aromatic solvents and halocarbon solvents.The organic moiety to which the ketone, and ether functional groups canbe attached includes alkyl, typically about C₁ to C₂₀, preferbly aboutC₁ to C₁₀, most preferably about C₁ to C₅ alkyl; aryl, typically aboutC₆ to C₁₄, preferably about C₆ to C₁₀, most preferably C₆ aryl;cycloalkyl, typically about C₄ to C₂₀, preferably about C₆ to C₁₂, mostpreferably about C₆ to C₁₀ cycloalkyl; aralkyl and alkaryl wherein thealkyl and aryl groups thereof are described above. Suitable keto ethersinclude molecules of the formula (V): ##STR5## wherein T¹ and T² areeach hydrocarbyl containing from 1 to 10 carbon atoms, and T³ isstraight or branched chain alkyl of from 1 to 6 carbon atoms.Illustrative of such keto ethers are CH₃ C(O)CH₂ CH₂ OCH₂ CH₃ ; C₃ H₇C(O)CH₃ H₆ OC₃ H₇ ; CH₃ C(O)CH₂ C(OCH₃)(CH₃)CH₃ ; CH₃ C(O)CH₂ C(OC₂H₅)(CH₃)CH₃ ; C₂ H₅ C(O)CH₂ CH₂ OC₄ H₉ ; and the like. Nitro-paraffinicsolvents include NO₂ -substituted alkanes of 2 to 5 carbon atoms.Halocarbon solvents include chloro- and fluoro-substituted saturatedhydrocarbons. Alcohol solvents include alkanols of 4 to 10 carbon atoms,and phenyl-substituted alkanols of 7 to 10 carbon atoms. Ether alcoholsinclude alkoxy-substituted alkanols of from 3 to 8 carbon atoms. Glycolsolvents include di-hydroxy substituted alkanes of from 2 to 6 carbonatoms. Glycol ether solvents include compounds of the formula R'--O--R"wherein R' is alkyl of from 1 to 6 carbon atoms, and R" ishydroxy-substituted alkyl of from 2 to 6 carbon atoms.

Suitable ester solvents comprise normally liquid C₁ to C₁₃ alkyl estersof alkanoic acids having from 2 to 7 carbon atoms. Prepared estersolvents are those selected from the group consisting of compoundshaving the formula (VI): ##STR6## wherein R¹ is a straight or branchedchain alkyl of from 1 to 6 carbon atoms, and R² is a straight orbranched chain alkyl of from 1 to 13 carbon atoms, with the proviso thatR¹ and R² together contain from 6 to 17 carbon atoms, and mixturesthereof. The "R¹ " group can also comprise C₂ to C₇ alkyl having onecarbon replaced by an ether oxygen (e.g., C₂ H₅ --O--C₂ H₄ --, C₃ H₇--O--C₂ H₄ --, CH₃ --O--C₂ H₄ --, C₂ H₅ --O--C₃ H₆ --, and the like).Exemplary of such ester solvents are butyl acetates, hexyl acetates,pentyl acetates, pentyl propionates, isobutyl isobutyrate, heptylacetates, methyl pentanoates, ethyl pentanoates, pentyl pentanoates,ethyl hexanoates, butyl hexanoates, ethyl neopentanoate, methylneoheptanoate, octyl acetates, nonyl acetates, decyl acetates, undecylacetates, dodecyl acetates, tridecyl acetates and the like. Exemplary ofesters wherein the carboxylc acid moiety is derived from anether-containing acid (e.g., acids which are alkoxy-substituted) areethyl 3-ethoxypropionate, butyl 3-butoxypropionate, methyl2-methoxyacetate, methyl 3-methoxypropionate, propyl 3-propoxypropionateand the like.

Especially preferred ester solvents of this invention are normallyliquid esters selected from the group consisting of compounds of theformula (VII): ##STR7## wherein R³ is a straight or branched-chain alkylhaving from 5 to 13 carbon atoms, and mixtures thereof. Exemplary ofsuch preferred ester solvents herein are pentyl acetates, hexylacetates, heptyl acetates, octyl acetates, nonyl acetates, decylacetates, undecyl acetates, dodecyl acetates, and tridecyl acetates. Theterm "normally liquid esters" as used herein is intended to refer toesters which are in the liquid state at ambient conditions (25° C., 1atm).

Suitable ketone solvents include methyl amyl ketone, methyl isobutylketone, methyl propyl ketone, isophorone, cyclohexanone, diethyl ketone,dibutyl ketone, methyl isopropyl ketone, methyl secbutylketone,benzophenone, mixtures thereof, and the like. Suitable ether solventsinclude dibutyl ether, tetrahydrofuran, anisole, dioctyl ether,1,2-dimethoxyethane, 1,4-dimethoxybutane. Suitable halocarbon solventsinclude 1,1,2-trichloroethane, tetrachloroethane and the like. Suitablenitroparaffinic solvents include nitropropane and nitroethane. Suitablealcohols include 2-ethyl hexanol, diacetone alcohol, phenethyl alcohol,benzyl alcohol, amyl alcohols, hexyl alcohols, heptyl alcohols, and thelike. Suitable glycol ethers, esters and mixed ether and ester solventsinclude ethylene glycol diacetate, propylene glycol diacetate,Cellosolve® acetate (registered trademark of the Union CarbideCorporation), butyl Cellosolve, Cellosolve, the Carbitols® (registeredtrademark of the Union Carbide Corporation), methoxy propyl acetate,ethoxy propyl acetate and the like. Suitable aromatic solvents comprisealkyl-substituted benzenes of the formula (VIII): ##STR8## wherein p isan integer of from 1 to 4, and X is in each instance in which it appearsindependently selected from the group consisting of straight andbranched-chain alkyl of from 1 to 4 carbon atoms.

Illustrative of suitable alkyl-substituted benzene solvents for use inthe solvent blends of this invention are ethyl benzene, isopropylbenzene, n-propyl benzene, 1-methyl-3-ethylbenzene,1-methyl-4-ethylbenzene, 1,3,5-trimethylbenzene,1-methyl-2-ethylbenzene, 1,2,4-trimethylbenzene, isobutylbenzene,sec-butylbenzene, 1-methyl-3-isopropylbenzene,1-methyl-4-isopropylbenzene, 1,2,3-trimethylbenzene,1-methyl-2-isopropylbenzene, 1,3-diethylbenzene,1-methyl-3-n-propylbenzene, n-butylbenzene, 1,4-diethylbenzene,1,3-dimethyl-5-ethylbenzene, 1,4-dimethyl-2-ethylbenzene,1,3-dimethyl-4-ethylbenzene, 1,2-dimethyl-4-ethylbenzene,1,2,4,5-tetramethylbenzene, 1,2,3,5-tetramethylbenzene and the like,toluene, xylene, cumene, alkyl-substituted benzenes in which the alkylsubstituent comprises a total of at least 2 carbon atoms when thebenzene ring is monoalkyl substituted and of at least 3 carbon atomswhen the benzene ring is substituted by two or more alkyl groups, andaromatic groups distributed by a cyclic aliphatic ring (e.g.,tetrahydronaphthalene), and mixtures of the foregoing.

The aromatic solvent component can also contain up to about 50 wt/%,preferably less than about 40 wt%, and more preferably up to about 25wt%, of other hydrocarbon solvents such as C₆ to C₁₁ aromatic solventsnot satisfying the definition of formula III above, as well as C₆ to C₁₁saturated aliphatic and cycloaliphatic hydrocarbons.

Especially preferred such polymerization solvents comprise from about 60to 90 wt% of an organic solvent (e.g., a normally liquid ester offormula VI) and from about 10 to 40 wt% of an aromatic solvent offormula VIII.

The polymerization solvents are preferably characterized by a normalboiling point (at 25° C., 1 atm) of at least about 100° C., morepreferably from about 115° to 250° C., and most preferably from about150° to 200° C. In addition, when the polymers of the present inventionare intended for use as a component of electrostatic spray coatings, thepolymerization solvents are preferably substantially free of water (morepreferably having a water content of less than 0.5 wt%) and trace metals(more preferably having a trace metals content of less than 0.004 wt%),and are characterized by a resistivity of at least 15 megohms, asdetermined by Ransburg resistivity meter.

In preparing the polymers of this invention, the selected monomers,including the desired hydroxy-substituted alkyl (meth)acrylate,non-hydroxy substituted alkyl (meth)acrylate and alpha-olefin, togetherwith any modifying or other monomers, may be mixed and reacted byconventional free radical initiated polymerization in the selectedpolymerization solvent in such proportions as to obtain the copolymerdesired. A large number of organic, free radical initiators are known inthe art and are suitable for the purpose. These include: benzoylperoxide; lauryl peroxide; t-butyl-hydroperoxide;acetylcyclohexylsulfonyl peroxide; di-isobutyryl peroxide;t-butyl-peroxypivalate; decanoyl peroxide;azobis-(2-methylpropionitrile); 2-t-butylazo-2-cyanobutane; tertiarybutyl perbenzoate, dicumyl peroxide, ethyl 3,3-(t-amylperoxy)butyrate,ethyl 3,3-di(t-butylperoxy) butyrate, t-butyl cumyl peroxide, anddi-(butyl cumyl) peroxide, and di-t-butyl peroxide, and other dialkylperoxides, peroxy ketals, and peroxyesters.

The total monomer mixture to be employed in preparing the polymersaccording to the process of this invention will generally comprise fromabout 30 to 95%, preferably from about 50 to 90 wt%, of the total massof monomers and solvent passed to the polymerization reaction vessel.Thus, the polymerization solvent will generally comprise from about 5 to70 wt%, preferably from about 10 to 50 wt%, of the total mass ofmonomers and solvent passed to the polymerization vessel. The quantityof free radical initiators employed as catalyst in the reaction can alsovary widely and will generally be present in an amount of from about 0.5to 10 wt% of the total monomer components charged to the reactionmixture.

The conditions of temperature and pressure for conducting thepolymerization reaction can vary widely. Generally, the polymerizationwill be conducted at a temperature of from about 100° to 240° C. (andpreferably from about 130° to 210° C.) at atmospheric pressure.Pressures of from about 10 to 500 psig are entirely suitable, althoughhigher or lower pressures can be employed. The polymerization reactioncan be carried out in any of the conventional equipment employed by theindustry for such reactions. Thus, the reaction vessel can comprise astirred reactor in which an inert atmosphere (e.g., N₂, Ar) ismaintained during the polymerizaton to avoid reactions with gaseousoxygen which compete, or interfere, with the desired polymerizationreaction. However, the improved high solids resins of the presentinvention can also be formed by a polymerization conducted in thepresence of air, thereby providing a polymerization process which is notcritically sensitive to equipment leaks or malfunctions whereby airenters into conventional process equipment.

In order to form resins of improved color, it is preferred that thepolymerization be conducted in the substantial absence of conjugatedolefinic impurities comprising conjugated diolefins; internallyunsaturated monoolefins in which the olefinic double bond is conjugatedwith an aromatic ring (e.g., as in indene); and internally unsaturatedmonoolefins which are alpha, beta unsaturated ketones, esters, amidesand acids. More preferably, the polymerization mixture contains lessthan 100 ppm of such conjugated olefinic impurities.

The polymerization process can be carried out batchwise,semi-continuously, or continuously. The monomers and solvent system canbe premixed or passed separately to the polymerization vessel alone, orin combination with the free radical initiators and other components. Inaddition, the components of the polymerization solvent may be premixedwith each other or with any other material to be charged (e.g., with anyof the monomers) or may be fed separately to the vessel.

The method of addition of the monomers can vary as described above, andis important in determining the final polymer composition. Morespecifically, the amount of alpha-olefin which is incorporated into thepolymer is dependent upon the method of monomer addition. Since thereactivity of the alpha-olefin is much less than the reactivity of theother monomers, a high concentration of the alpha-olefin relative to theother monomers in the reaction zone is beneficial for incorporation of asignificant amount of alpha-olefin into the polymer structure.Accordingly, when high alpha-olefin incorporation is desired, it isdesirable to combine a large portion of the alpha-olefin with the massof the polymerization solvent and introduce this solution to thereaction vessel separately from and prior to the introduction of theremaining monomers (e.g., Monomers A, B, and D and the balance of thealpha-olefin monomer). Depending on the desired amount of alpha-olefinincorporation into the polymer, the initial amount of alpha-olefincombined with the polymerization solvent can be adjusted, with thebalance of the alpha-olefin combined with the other monomers. Generally,the higher the amount of alpha-olefin initially added to thepolymerization solvent, the greater the alpha-olefin incorporation intothe polymer structure.

Another method to increase the alpha-olefin incorporation into thepolymer is to increase the addition time of the other monomers therebyincreasing the relative concentration of the alpha-olefin relative tothe other monomers.

In one embodiment of the process of this invention, substantially all ofthe solvent is added to the reaction flask and is heated to the desiredreaction temperature. At this point, an addition of substantially all(i.e., at least about 80 wt%) of the monomer is begun. Minor amounts ofone or more of the monomers; i.e., up to about 20 weight percent of thetotal monomer weight may be placed in the reaction vessel with thesolvent. The addition is carried out over at least about 30 minutes. Notall of the monomers need be mixed together; rather, separate additionsof different monomers or different ratios of different monomers, may beused. Preferably, the addition time should be in the range of about 1 to15 hours, most preferably 2 to 10 hours.

In a preferred embodiment of the process of this invention, from about10 to 100 wt% (and more preferably from at least about 80 wt%, and mostpreferably at least about 90 wt%) of the alpha-olefin monomer iscombined with the mass of the polymerization solvent and introduced tothe reaction vessel separately from (and preferably prior to) theintroduction of the remaining monomers (e.g., Monomers A, B and D, andthe balance of the alpha-olefin monomer), and the balance of thealpha-olefin is charged to the reaction vessel along with the other suchmonomers.

The initiators which are utilized in the instant invention may be eithermixed with the monomer or added separately over the general period ofthe monomer addition. In view of the high reaction temperature involved,addition of any major amount of the initiator to the solvent prior tothe addition of the monomer will be of little or no effect.

Addition times of both initiators and monomers may vary and the variousmonomers may be added over regular periods of time, periodically, orover gradually increasing or decreasing periods of time, as long as thetotal amount of monomer addition is substantially within the rangesindicated.

The initiator should be added to the reaction over at least 30 minutesand preferably over the same or longer period of time that Monomers A, Band D are added. This can be accomplished, for example, by introducingthe initiator to the reaction vessel simultaneously with the monomerfeed, followed by the introduction of an additional amount of theinitiator (generally from about 5 to 30 wt% of the total initiator to becharged) with stirring, to bring the polymerization of any remainingmonomers to completion. Initiator levels should vary from about 0.5percent to 10 percent, based on the total monomer weight, preferably 0.5to 5 percent.

The time for which the polymerization reaction is allowed to proceed canalso vary widely and will generally range from about 0.5 to 15 hours,preferably from about 1 to 10 hours.

Reaction temperature should be maintained within the desired temperatureranges following monomer addition for a time sufficient to causeconversion of all the monomer to polymer. This is usually measured bydetermining the solids content of the reaction mixture by measuring theamount of solvent that evaporates, when test samples are held for thedesired time at the selected temperature (e.g., for about 20 minutes at220° C.). The term "solids content" does not refer to whether thepolymer prepared herein is liquid or solid in nature, but rather refersto the amount of material which is left behind after the evaporation atthe selected conditions. Thus, the term "solids content" is synonymouswith the term "percent non-volatile matter" or "percent NVM" at theselected conditions.

At this point, the reaction solvent may be removed by either increasingthe heat or applying a vacuum or both. It is preferred that vacuum beutilized in addition to heat to minimize heat degradation of thepolymer. Alternatively, and more preferably, the solvent can remain withthe polymer resins for formulation of coatings therefrom, as will bedescribed more completely below.

The acrylic resins produced by the process of this invention arepreferably liquid in nature and characterized by weight averagemolecular weights (M_(w)) from about 800 to 15,000, and more preferablyfrom about 1,000 to 10,000, and most preferably from about 1,000 to8,000. Also, the acrylic resins produced by the process of thisinvention are preferably characterized by number average molecularweights (M_(n)) falling within a range of from about 500 to 8,000, andmore preferably from about 700 to 5,500, and by M_(w) /M_(n) ratios offrom about 2 to 5, and more typically from about 2 to 4. Furthermore,the acrylic resins of the present invention will be preferablycharacterized by kinemmatic viscosities at 65% NVM of up to 10,000 cs,and more preferably from about 100 to 5,000 cs (as determined by ASTMD445). These acrylic resins can then be employed in the formulation ofcoatings with or without the addition of other solvents. The componentsof such coating compositions formulated using these acrylic resins canbe any of the conventional crosslinking agents, catalysts, antioxidants,UV absorbers and stabilizers, surface modifiers, wetting agents as wellas pigments. These materials are conventional and a more completedescription thereof is not necessary for a full understanding of thisinvention. For example, illustrative conventional UV absorbers andstabilzers are illustrated by those discussed in European PatentApplication No. 29,594.

The coatings prepared by use of the acrylic resins of this invention canbe applied to substrates, such as automobiles and the like, usingconventional methods known to the art, such as roller coating, spraycoating, electrostatic spray coating, dipping or brushing. Of course,the particular application technique will depend on the particularsubstrate to be coated and the environment in which the coatingoperation is to take place. A particularly preferred technique forapplying the high solids compositions, particularly when applying thesame to automobiles as top coats, is spray coating through the nozzle ofa spray gun.

In accodance with another embodiment of the present invention, animproved method for formulating a high solids acrylic resin coating,intended for use in electrostatic spray applications, is providedwherein the acrylic resin, which is formed by conventional techniques orby use of the aforementioned improved polymerization process, isformulated into a high solids coating by use of a cutting solventcomprising a mixture of any of the above-discussed solvents, with orwithout one or more of the alphaolefins of formula (I). The coatingcomposition is preferably formulated to contain high solids (that is, atleast about 50 wt% solids) and preferably from about 50 to 90 wt%solids, and most preferably from about 55 to 80 wt% solids.

As with the previously discussed embodiment of this invention, theacrylic resin coatings of this invention can be employed in combinationwith any of the conventional cross-linking agents, catalysts,anti-oxidants, UV absorbers and stabilizers, surface modifiers, wettingagents and pigments which are known in the art. These materials, again,are conventional and a more complete description thereof is notnecessary for full understanding of this invention. For example,illustrative conventional UV absorbers and stabilizers are thoseillustrated by the discussion of European Patent Application No. 29,594and by the surface modifiers and pigments described in European PatentApplication No. 29,339, the disclosures of which are hereby incorporatedby reference.

The novel coating compositions of this invention can be applied to avariety of substrates such as metal, wood, glass, and plastics such aspolystyrene, polyurethane and copolymers of styrene, by any of the usualapplication methods such as by spraying, electrostatic spraying,dipping, brushing, flow coating, rolling and the like. Most preferably,the novel coating compositions of this invention are applied byelectrostatic spraying.

The thus-formed coatings can be air-dryed or baked. The resultingcoating is preferably from about 0.2 to 3 mils thick, and preferably 0.4to 2.5 mils thick, and can be rubbed or polished in accordance withconventional techniques, if desired, to improve smoothness or apparentgloss or both.

After the novel coating composition is applied, the coating ispreferably cured at about 80° to 250° C. for about 1 to 45 minutes.

While the acrylic resins of this invention have been described above foruse in coatings, it will also be understood that such low molecularweight resins may be used in any of a varied number of end applications.For example, they may be used as plasticizers for rigid, inflexiblepolymeric systems. In addition, they may be utilized in combination withconventional curing agents to form films and plastic articles, and asbinders and sizers. Examples of the curing agents which may be utilizedfor preparing cross-linked polymeric products including polyepoxides,di-isocyanates and urea-aldehyde, benzoguanaminealdehyde, ormelamine-aldehyde condensation products and the like. Particularlydesired are the melamine-formaldehyde condensation products, such aspolymethoxymethyl melamines, preferably the hexamethoxymethyl melamines.When malamine-formaldehyde or urea-formaldehyde curing agents areutilized, it is preferred that an acid catalyst (such as butyl acidphosphate, paratoluene sulfonic acid, naphthalene sulfonic acid,napthalene di-sulfonic acids and dodecyl benzene sulfonic acid [asdescribed in U.S. Pat. Nos. 3,979,478 and 4,075,176], and amine salts ofany of the foregoing) be employed to increase the cure rate.

The process and compositions of this invention can be furtherillustrated by reference to the following examples, wherein parts are byweight unless otherwise indicated.

In the Examples, unless otherwise indicated, the following testprocedures or devices were used for determining the correspondingproperties:

                  TABLE 1                                                         ______________________________________                                        Property Measurement                                                                            Test Method/Device                                          ______________________________________                                        Viscosity         Brookfield model HAT                                                          synchro-electric                                                              viscometer                                                  Electrical Resistivity                                                                          Ransburg 5650 paint                                                           resistance tester (manu-                                                      factured by Ransburg)                                       Color             Pt/Co scale, Spectro-                                                         metric measurements                                                           using Beckman DB67 grat-                                                      ing spectro-photometer                                                        (ASTM D1209-79)                                             ______________________________________                                    

The hexylacetate and heptylacetate used in the Examples were products ofan esterification reaction between acetic acid and the correspondinghexyl or heptyl alcohol. The alcohol precursors themselves were formedin a commercial oxo reaction and each comprised a mixture of normal- andiso-alcohols. (Similar results would be achieved if pure normal- oriso-hexyl or heptyl alcohols were used.)

In the Examples, AROMATIC® 100 solvent (manufactured by Exxon Company,U.S.A.) comprised of a narrow-cut aromatic solvent containing about 40wt% trimethyl benzenes, 35 wt% methyl ethyl benzenes, 10 wt% propyl andisopropyl benzenes, 3 wt% ethyl dimethyl benzenes, 2 wt% methyl (n- andiso-) propyl benzenes, 2 wt% diethyl benzenes, <1 wt% each of mono butylbenzenes and tetramethyl benzenes, 6 wt% xylenes and minor amounts ofethyl benzene, C₁₀ and C₁₁ saturates and unknowns. AROMATIC® 150 solvent(manufactured by Exxon Company U.S.A.) comprised a narrow-cut aromaticsolvent containing about 23 wt% tetra-methyl benzenes, 22 wt% ethyldimethyl benzenes, 15 wt% mono-, di- and tri-methyl indanes, 8 wt%diethyl benzenes, 8 wt% naphthalenes, 5 wt% trimethyl benzenes, 2 wt%indane, and about 1 wt% or less of methyl ethyl benzenes, propylbenzenes, methyl propyl benzenes, butyl benzenes, hexyl benzenes,indene, methyl naphthalenes, xylenes, and unknowns.

Number average molecular weights (M_(n)) and weight average molecularweights (M_(w)) were found by gel permeation, with a polystyrenestandard (using a Waters GPC-1 instrument).

Non-volatile matter (NVM) measurements were made by mixing a weighedsample of the product resin-polymerization solution with sufficienttoluene to produce a 10:90 wt:wt resin product solution:toluene mixtureand thereafter casting a thin film (about 0.05 mm) which was baked onehour at 150° C. in air, followed by weighing the residual material.

EXAMPLE 1

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 688 g ofheptylacetate together with 344 g of 1-decene. Nitrogen was continuouslyblown into the apparatus at a slow rate. The solvent plus 1-decene washeated over a 0.5 hour period to 160° C. polymerization temperature. Amixed liquid feed, comprising a blend of 240 g styrene, 1136 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, and the initiator, 24 g oftert-butyl peroxide were placed into a separate one gallon container.The monomer plus initiator solution was pumped to the reaction flaskover a 187 minute period at 160° C. with continual stirring and N₂ flow.After the addition was complete, the reaction mixture was stirred for anadditional 23 minutes at 160° C. Then an additional 12 g tert-butylperoxide was added and the mixture stirred at 160° C. temperature foranother 1.5 hours. The reaction mixture then was cooled with stirringand analyzed. The resin formed had:

    ______________________________________                                        Viscosity (cps)    21,000                                                     Color (Pt/Co)      30.0                                                       Mn                 5,700                                                      Mw                 14,700                                                     Mw/Mn              2.6                                                        % 1-decene in polymer                                                                            12.4                                                       1-decene conversion, %                                                                           ˜100                                                 ______________________________________                                    

This example has demonstrated essentially complete incorporation of1-decene into the copolymer.

EXAMPLE 2

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 1032 g ofheptyl acetate solvent. N₂ was slowly blown into the apparatuscontinually. The solvent was heated over a 0.5 hour period to 160° C.polymerization temperature. The mixed monomer feed, comprising a blendof 240 g styrene, 896 g of butyl acrylate, 480 g each of 2-hydroxyethylmethacrylate and methyl methacrylate, 64 g of acrylic acid, 240 g1-decene, and the initiator, 24 g of tert-butyl peroxide, were placedinto a separate one gallon container. The monomer plus initiatorsolution was pumped to the reaction flask over a 180 minute period at160° C. with continual stirring and N₂ flow. After the monomer blend wasadded, the reaction mixture was stirred an additional 60 minutes at thepolymerization temperature. Then an additional 12 g tert-butyl peroxidewas added and the mixture stirred at 160° C. temperature for another 1.5hours. The reaction mixture then was cooled with stirring and analyzed.The resin formed had:

    ______________________________________                                        NVM (%)            68.1                                                       Viscosity (cps)    8,100                                                      Color (Pt/Co)      35                                                         Mn                 3,690                                                      Mw                 10,390                                                     Mw/Mn              2.8                                                        % 1-decene in polymer                                                                            7.0                                                        1-decene coversion 69.6                                                       ______________________________________                                    

This example has demonstrated reduced incorporation 1-decene incopolymer when 1-decene was mixed with the monomer feed.

EXAMPLE 3

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 778 g ofheptyl acetate solvent N₂ was slowly blown into the apparatuscontinually. The solvent was heated over a 0.5 hour period to 160° C.polymerization temperature. The mixed monomer feed, comprising a blendof 240 g styrene, 896 g of butyl acrylate, 480 g each of 2-hydroxyethylmethacrylate and methyl methacrylate, 64 g of acrylic acid, and 240 g of1-decene, was placed into a separate one gallon container and 36 g oft-butyl perbenzoate initiator in 254 g heptyl acetate solvent was placedin a separate container. The monomer feed and initiator solutions wereseparately pumped to the reaction flask at 160° C. with continualstirring and N₂ flow. The monomer addition time was 187 minutes and theinitiator addition time was 240 minutes. When the addition was complete,the reaction mixture was stirred an additional hour at 160° C. Then thereaction mixture was cooled and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            67.5                                                       Viscosity (cps)    11,750                                                     Color (Pt/Co)      20                                                         Mn                 2,100                                                      Mw                 10,400                                                     Mw/Mn              5                                                          % 1-decene in polymer                                                                            6.2                                                        1-decene conversion, %                                                                           61                                                         ______________________________________                                    

EXAMPLE 4

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 994 gheptyl acetate solvent together with 200 g of 1-decene. N₂ was slowlyblown into the apparatus continually. The solvent plus decene wereheated over a 0.5 hour period to 160° C. polymerization temperature. Themixed monomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, 300 g 1-decene, and the initiator,48 g tert-butyl peroxide, were placed into a one gallon container. Thismonomer plus initiator solution was pumped to the reaction flask at 160°C. with continual stirring and N₂ flow. The initial rate of addition wasapproximately 500 ml over a 30 minute period, followed by the balance ofthe amount over 165 minutes. After the monomer blend was added, thereaction mixture was stirred for an additional 30 minutes at thepolymerization temperature. Then a second charge containing 12 gtert-butyl peroxide initiator in 38 g Aromatic® 150 solvent and 50 gheptyl acetate was added to the reaction flask over a 70 minute periodat 160° C., with continual stirring and N₂ flow. When the secondaddition was complete, the reaction mixture was stirred an additional 30minutes at 160°. The reaction mixture was then cooled with stirring andanalyzed. The resin formed had:

    ______________________________________                                        NVM (%)            64.3                                                       Viscosity (cps)    2,130                                                      Color (Pt/Co)      14                                                         Mn                 2,660                                                      Mw                 7,470                                                      Mw/Mn              2.8                                                        % 1-decene in polymer                                                                            12.8                                                       1-decene conversion, %                                                                           57.3                                                       ______________________________________                                    

EXAMPLE 5

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermoeter, was charged 944 g heptylacetate solvent together with 200 g of 1-decene. N₂ was slowly blowninto the apparatus continually. The solvent plus decene were heated overa 0.5 hour period to 160° C. polymerization temperature. The mixedmonomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, 300 g 1-decene, and the initiator,48 g tert-butyl peroxide, were placed into a separate one galloncontainer. The monomer plus initiator solution was pumped to thereaction flask over a 300 minute period at 160° C. with continualstirring and N₂ flow. The initial rate of addition was approximately 500ml over a 30 minute period, followed by the balance of the amount over270 minutes. After the addition was completed, the reaction mixture wasstirred an additional 30 minutes. Then a second charge containing 12 gtert-butyl peroxide initiator in 38 g Aromatic® 150 and 50 g heptylacetate was added to the flask over a 75 minute period at 160° C. withcontinual stirring and N₂ flow. When the second addition was complete,the reaction mixture was stirred an additional 30 minutes at 160° C.,and then cooled and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            64.8                                                       Viscosity (cps)    1,640                                                      Color (Pt/Co)      20                                                         Mn                 1,860                                                      Mw                 6,280                                                      Mw/Mn              3.4                                                        % 1-decene in polymer                                                                            13.4                                                       1-decene conversion                                                                              60.8                                                       ______________________________________                                    

EXAMPLE 6

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 944 gheptyl acetate solvent together with 100 g 1-decene. N₂ was slowly blowninto the apparatus continually. The solvent plus decene was heated overa 0.5 hour period to 160° C. polymerization temperature. The mixedmonomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, 400 g 1-decene, and the initiator,48 g butyl peroxide, were placed into a one gallon container. Themonomer plus initiator solution was pumped to the reaction flask over a288 minute period at 160° C. with continual stirring with N₂ flow. Theinitial rate of addition was approximately 633 ml over a 38 minuteperiod, followed by the balance of the amount over 250 minutes. Afterthe addition was completed, the reaction mixture was stirred anadditional 30 minutes. Then a second charge containing 12 g tert-butylperoxide initiator in 38 g Aromatic® 150 solvent and 50 g heptyl acetatewas added to the flask over a 70 minute period at 160° C. with continualstirring and N₂ flow. When the second addition was complete, thereaction mixture was stirred an additional 30 minutes at 160° C., andthen cooled and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            63.5                                                       Viscosity (CPS)    1,050                                                      Color (PT/CO)      16.5                                                       Mn                 2,610                                                      Mw                 5,260                                                      Mw/Mn              2.0                                                        % 1-decene in polymer                                                                            11.6                                                       1-decene conversion                                                                              51.7                                                       ______________________________________                                    

EXAMPLE 7

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 994 gheptyl acetate solvent together with 100 g of 1-decene. N₂ was slowlyblown into the apparatus continually. The solvent plus decene was heatedover a 0.5 hour period to 165 polymerization temperature. The mixedmonomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, 400 g of 1-decene, and theinitiator, 48 g of tert-butyl peroxide, were placed into one galloncontainer. The monomer plus initiator solution was pumped to thereaction flask over a 360 minute period at 165° C. with continualstirring and N₂ flow. The initial rate of addition was approximately1,000 ml over a 60 minute period, followed by the balance of the amountover 300 minutes. After the addition was complete, the reaction mixturewas stirred an additional 30 minutes. Then a second charge containing 12g tert-butyl peroxide initiator in 38 g Aromatic® 150 solvent, and 50 gheptyl acetate was added to the flask over a 75 minute period at 165° C.with continual stirring and N₂ flow. When the second addition wascomplete, the reaction mixture was stirred and additional 30 minutes at165° C., and then cooled and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            63.9                                                       Viscosity (cps)    980                                                        Color (Pt/Co)      18.5                                                       Mn                 2,130                                                      Mw                 6,210                                                      Mw/Mn              2.9                                                        % 1-decene in polymer                                                                            12.2                                                       1-decene conversion                                                                              54.5                                                       ______________________________________                                    

EXAMPLE 8

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 944 gheptyl acetate solvent together with 100 g of 1-decene. N₂ was slowlyblown into the apparatus continually. The solvent plus decene wereheated over a 0.5 hour period to 160° C. polymerization temperature. Themixed monomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, 400 g of 1-decene, and theinitiator, 48 g of tert-butyl peroxide, were placed into a one galloncontainer. The monomer plus initiator solution was pumped to thereaction flask over a 345 minute period at 160° C. with continualstirring and N₂ flow. The initial rate of addition was approximately1,000 ml over a 60 minute period, followed by the balance of the amountover 285 minutes. After the addition was completed, the reaction mixturewas stirred an additional 30 minutes. Then a second charge containing 12g tert-butyl peroxide initiator in 38 g Aromatic® 150 solvent and 50 gheptyl acetate was added to the flask over a 70 minute period at 160° C.with continual stirring and N₂ flow. When the second addition wascomplete, the reaction mixture was stirred an additional 30 minutes at160° C., and then cooled and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            64.8                                                       Color (Pt/Co)      19                                                         Mn                 2,930                                                      Mw                 8,820                                                      Mw/Mn              3.6                                                        % 1-decene in polymer                                                                            13.4                                                       1-decene conversion                                                                              60.8                                                       ______________________________________                                    

EXAMPLE 9

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 832 gheptyl acetate solvent together with 300 g 1-decene. N₂ was slowly blowninto the apparatus continually. The solvent plus decene were heated overa 0.5 hour period to 170° C. polymerization temperature. The mixedmonomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, and 200 g 1-decene were placed intoa separate one gallon container and 60 g of tert-butyl peroxide asinitiator in 100 g Aromatic® 150 solvent and 100 g heptyl acetatesolvent was placed in a separate container. The monomer feed andinitiator solutions were separately pumped too the reaction flask at170° C. with continual stirring and N₂ flow. The monomer mixture wasadded at the rate of about 1,000 ml during the first 1/2 hour, and therest at the rate of 250 ml/hr over 330 minutes. The initiator solutionwas added continuously over a 480 minute period time period. Thereaction mixture then was cooled with stirring and analyzed. The resinformed had:

    ______________________________________                                        NVM (%)            66.9                                                       Viscosity (cps)    740                                                        Color (Pt/Co)      17.5                                                       % 1-decene in polymer                                                                            16.1                                                       1-decene conversion                                                                              75.5                                                       ______________________________________                                    

This example has demonstrated essentially complete incorporation of1-decene into the copolymer.

EXAMPLE 10

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 832 gheptyl acetate solvent together with 300 g 1-decene. N₂ was slowly blowninto the apparatus continually. The solvent plus decene were heated overa 0.5 hour period to 170° C. polymerization temperature. The mixedmonomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid and 200 g 1-decene were placed into aone gallon container and 60 g of tert-butyl peroxide as initiator in 100g of Aromatic® 150 solvent and 100 g of heptyl acetate solvent wasplaced in a separate container. The monomer feed and initiator solutionswere separately pumped to the reaction flask at 170° C. with continualstirring and N₂ flow. The monomer mixture was added at the rate of about1,000 ml/hour during the first 1 hour, and the rest at the rate of 250ml/hour over a 230 minute time period. The initiator solution was addedcontinuously over a 415 minute time period. The reaction mixture thenwas cooled with stirring and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            66.5                                                       Viscosity (cps)    1,000                                                      Color (Pt/Co)      16                                                         Mn                 5,700                                                      Mw                 14,700                                                     Mw/Mn              2.6                                                        % 1-decene in polymer                                                                            15.6                                                       1-decene conversion                                                                              72.7                                                       ______________________________________                                    

EXAMPLE 11

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, and air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 832 gheptyl acetate solvent together with 400 g of 1-decene. N₂ was slowlyblown into the apparatus continually. The solvent plus decene wereheated over a 0.5 hour period to 170° C. polymerization temperature. Amixed monomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid and 100 g 1-decene were placed into aseparate one gallon container and 60 g of tert-butyl peroxide asinitiator in 100 g of Aromatic® 150 solvent and 100 g heptyl acetatesolvent was placed in a separate container. The monomer feed andinitiator solutions were separately pumped to the reaction flask at 170°C. with continual stirring and N.sub. 2 flow. The monomer mixture wasadded at the rate of about 1,000 ml/hour during the first one hour, andthe rest at the rate of 250 ml/hour over a 215 minute time period. Theinitiator was added continuously over a 410 minute time period. Thereaction mixture then was cooled with stirring and analyzed. The resinformed had:

    ______________________________________                                        NVM (%)            66.5                                                       Viscosity (cps)    1,060                                                      Color (Pt/Co)      18.5                                                       % 1-decene in polymer                                                                            15.6                                                       1-decene conversion                                                                              72.7                                                       ______________________________________                                    

EXAMPLE 12

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 672 gheptyl acetate solvent together with 400 g of 1-decene. N₂ was slowlyblown into the apparatus continually. The solvent plus decene wereheated over a 0.5 hour period to 170° C. polymerization temperature. Themixed monomer feed, comprising a blend of 400 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid and 100 g 1-decene were placed into aseparate one gallon container and tert-butyl peroxide in initiator in100 g Aromatic® 150 and 100 g heptyl acetate solvent was placed in aseparate container. The monomer feed and initiator solutions wereseparately pumped to the reaction flask at 170° C. with continualstirring and N₂ flow. The monomer mixture was added at the rate of about1,000 ml/hour during the first hour and the rest at the rate of 250ml/hour over a 225 minute time period. The initiator solution was addedcontinuously over a 405 minute time period, and therefore stirring atpolymerization was continued. The reaction mixtures then was cooled withstirring and analyzed. The resin formed had:

    ______________________________________                                        NVM (%)            69.7                                                       Viscosity (cps)    3,300                                                      Color (Pt/Co)      17.9                                                       Mn                 2,130                                                      Mw                 7,680                                                      Mw/Mn              3.6                                                        % 1-decene in polymer                                                                            12.9                                                       1-decene conversion                                                                              62.9                                                       ______________________________________                                    

EXAMPLE 13

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 944 gheptyl acetate solvent together with 200 g 1-hexadecene. N₂ was slowlyblown into the apparatus continually. The solvent plus hexadecene wereheated over a 0.5 hour period to 160° C. polymerization temperature. Themixed monomer feed, comprising a blend of 240 g styrene, 636 g of butylacrylate, 480 g each of 2-hydroxyethyl methacrylate and methylmethacrylate, 64 g of acrylic acid, 300 g of 1-decene, and theinitiator, 48 g tert-butyl peroxide, were placed into a one galloncontainer. The monomer plus initiator solution was pumped to thereaction flask over a 300 minute period at 160° C. with continualstirring and N₂ flow. The initial rate of addition was approximately 500ml over a 30 period, followed by the balance of the amount over 270minutes. After the addition was completed the reaction mixture wasstirred an additional 30 minutes. Then a second charge containing 12 gtert-butyl peroxide initiator in 38 g Aromatic® 150 solvent and 50 gheptyl acetate was added to the flask over a 75 minute period at 160° C.with continued stirring and N₂ flow. When the second addition wascomplete, the reaction mixture was stirred an additional 30 minutes at160° C., and then cooled and analyzed. The reaction mixture was thencooled with stirring. The resin formed had:

    ______________________________________                                        NVM (%)            65.1                                                       Viscosity (cps)    2,600                                                      Color (Pt/Co)      18.5                                                       Mn                 2,670                                                      Mw                 7,670                                                      Mw/Mn              2.6                                                        % 1-decene in polymer                                                                            62.9                                                       1-decene conversion                                                                              13.8                                                       ______________________________________                                    

This example has demonstrated essentially complete incorporation of1-decene into the copolymer.

COMPARATIVE EXAMPLE 14

The procedure of Example 11 was repeated using a monomer mixturecomprising 240 g styrene, 636 g butyl acrylate, 480 g 2-hydroxyethylmethacrylate, 480 g methyl methacrylate, 64 g acrylic acid and 100 gdecane (instead of 1-decene), and using 50 g tertiary butyl peroxideinitiator in 840 g heptyl acetate to which 400 g decane was added in thereaction vessel prior to feeding the monomer mixture. The polymerizationwas carried out in the following sequence at polymerization conditions:monomer mixture added over 305 minutes time period; continued stirring;additional initiator feed (10 g tertiary butyl peroxide in 30 g AROMATIC150® solvent) begun at 310 minutes and concluded at 365 minutes; stirredfor additional 30 minutes, for a total polymerization time of 395minutes.

Phase separation of the polymer and solvent phases were observedthroughout the reaction, and the lower resin phase was observed to becloudy with suspended resin solids distributed in the lower layer.

EXAMPLE 15

To a four-necked, five liter round bottomed flask fitted with a oneliter dropping funnel, a water jacketed reflux condenser, an air drivenstirrer (made of 316 stainless steel) and a thermometer, was charged 512g of hexyl acetate as polymerization solvent, together with 128 g of2,4,4-trimethyl-1-pentene (TMP) monomer. Air was blown into theapparatus at the rate of 8 cc/min, and stirring at 250 RPM wascommenced. The solvent was heated over a 0.5 hour period to 140° C. Ablend of 480.0 g styrene, 480.0 g butyl acrylate, 240.0 g 2-hydroxyethylmethacrylate and 6 wt% of t-butyl perbenzoate as initiator (based ontotal weight of the monomers and initiator), was placed in the droppingfunnel and added to the polymerization solvent with stirring and at themetered air-flow over a three hour period. Temperature was maintainedbetween 138°-145° C. After all the monomer blend was added, the reactionmixture was stirred for an additional 30 minutes at 140° C. At thispoint a final amount of 6.0 g of t-butyl perbenzoate in 6.0 g of hexylacetate was added slowly and the mixture stirred at 140° C. for a finaltwo hours.

The data thereby obtained indicated the polymer resin so produced had aPt/Co color of 20, a viscosity of 3700 cps, and contained 69.1% NVM. TheTMP conversion was 51%, and there was 4.9 wt% TMP incorporated into thepolymer.

When this experiment was repeated without the TMP monomer, the resultingresin had a Pt/Co color of 28, a resin viscosity of 2880 cps, and only65.7% NVM.

EXAMPLE 16

To a four-necked, five liter round bottomed flask fitted with two liquidfeed tubes, a water jacketed reflux condenser, an air driven stirrer(made of 316 stainless steel) and a thermometer, was charged 650 g ofheptyl acetate solvent together with 1195 g of 1-decene. N₂ was slowlyblown into the apparatus continually. The solvent plus dodecene wereheated over a 0.5 hour period to 160° C. polymerization temperature. Themixed monomer feed, comprising a blend of 1140 g of methyl methacrylate,and 360 g of acrylic acid were placed into a one gallon container and 65g of tert-butyl peroxide as initiator in 20 g heptyl acetate and 80 gAromatic® 100 solvent was placed in a separate 200 ml container. Themonomer feed and initiator solutions were separately pumped to thereaction flask at 160° C. with continual stirring and N₂ flow. Themonomer mixture was added at the rate of about 250 ml/hour over 340minutes. The initiator solution was added continuously over a 400 minuteperiod of time. The reaction mixture then was cooled with stirring andanalyzed. The resin formed had:

    ______________________________________                                        NVM (%)            63.9                                                       Viscosity (cps)    14,200                                                     1-decene conversion                                                                              55.4                                                       % 1-decene in polymer                                                                            30.0                                                       ______________________________________                                    

It will be obvious that various changes and modifications may be madewithout departing from the invention and it is intended, therefore, thatall matter contained in the foregoing description shall be interpretedas illustrative only and not limitative of the invention.

What is claimed is:
 1. Improved acrylic resins, which comprise resinsformed by polymerization of from about 30 to 95 wt.% of an acrylicmonomer mixture in the presence of from about 5 to 70 wt.% of apolymerization solvent, said acrylic monomer mixture comprising:(i) fromabout 5 to 45 wt.% of at least one member selected from the groupconsisting of hydroxy-substituted alkyl (meth)acrylates, acrylic acidand methacrylic acid; (ii) from about 20 to 80 wt.% of at least onemember selected from the group consisting of non-hydroxy substituted C₁-C₄ alkyl methacrylates and vinyl aromatic hydrocarbons; (iii) fromabout 0.5 to 6 wt.% of at least one free radical polymerizationinitiator; (iv) from about 1 to 55 wt.% of at least one alpha-olefinmonomer selected from the group consisting of aliphatic alpha-olefins offrom 7 to 20 carbon atoms; and (v) from about 0 to 64 wt.% of at leastone alkyl ester of acrylic acid, with the proviso that the sum ofmonomers (i) and (ii) comprise at least about 35 wt.% of said monomermixture.
 2. The resins of claim 1 wherein said hydroxy-substituted alkyl(meth)acrylate monomer comprises a member selected from the groupconsisting of monomers of the formula: ##STR9## wherein R⁴ is hydrogenor methyl and R⁵ and R⁶ are independently selected from the groupconsisting of hydrogen and alkyl of from 1 to 6 carbon atoms.
 3. Theresins of claim 1 wherein said polymerization solvent comprises at leastone member selected from the group consisting of ketones, esters, ketoethers, ethers, alcohols, glycols, glycol ethers, glycol esters, mixedglycol ether esters, aromatic solvents, halocarbon solvents andnitroparaffinic solvents.
 4. The resins of claim 3 wherein saidpolymerization solvent is characterized by a normal boiling point of atleast about 100° C.
 5. The resins of claim 3 wherein said polymerizationsolvent comprises at least one ester of the formula: ##STR10## whereinR' is a straight or branched chain alkyl of from about 1 to 6 carbonatoms, and R" is a straight or branched chain alkyl of from about 1 to13 carbon atoms, with the proviso that R' and R" together contain from 5to 17 carbon atoms.
 6. The resins of claim 5 wherein said ester solventis employed in admixture with at least one alkyl-substituted benzenesolvent.
 7. The resins of claim 6 wherein said alkyl-substituted benzenesolvent comprises at least one aromatic compound of the formula:##STR11## wherein p is an integer of from 1 to 4, and X is in eachinstance in which it appears independently selected from the groupconsisting of straight and branched-chain alkyl of from 1 to 4 carbonatoms.
 8. The resins of claim 1 wherein the acrylic polymer produced insaid polymerization reaction is characterized by a weight averagemolecular weight of from about 800 to about 15,000, and by anon-volatile matter content of at least 60 wt%.
 9. The resins of claim 1wherein said alpha-olefin comprises at least one linear or branchedaliphatic olefin having from 7 to 20 carbon atoms per molecule.
 10. Theresins of claim 9 wherein said alpha-olefin comprises at least onemember selected from the group consisting of 1-octene, 1-nonene,1-undecene, 1-decene, 1-dodecene, 1-tridecene, and 1-tetradecene.